CN105949382B - A kind of biological antibiotic type acrylic resin and the marine antifouling coating compositions using its preparation - Google Patents

A kind of biological antibiotic type acrylic resin and the marine antifouling coating compositions using its preparation Download PDF

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CN105949382B
CN105949382B CN201610454744.XA CN201610454744A CN105949382B CN 105949382 B CN105949382 B CN 105949382B CN 201610454744 A CN201610454744 A CN 201610454744A CN 105949382 B CN105949382 B CN 105949382B
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acrylic resin
type acrylic
biological antibiotic
azobisisovaleronitrile
resin
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CN105949382A (en
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陆阿定
宋伟
胡建坤
李娟�
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Zhejiang Marine Development Research Institute
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Zhejiang Marine Development Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a kind of antifouling paint, more particularly to a kind of biological antibiotic type acrylic resin and the novel sea antifouling paint compositions using its preparation.A kind of biological antibiotic type acrylic resin, the resin are made by the raw material as follows in terms of mass fraction：Azodiisobutyronitrile 0.35 0.45%, azobisisovaleronitrile 0.38 0.48%, lauryl mercaptan 0.49 1.2%, butyl acetate 47 50%, hydroxy-ethyl acrylate 2.3 3.6%, acrylic acid trichlorine phenyl ester 9 10%, butyl acrylate 24 28%, isobornyl acrylate 10 13%.It is a kind of environmentally friendly biological antibiotic type antifouling paint without copper Wuxi in inventive formulation system.

Description

A kind of biological antibiotic type acrylic resin and the marine antifouling coating group using its preparation Close object
Technical field
The present invention relates to a kind of antifouling paint, more particularly to a kind of biological antibiotic type acrylic resin and using its preparation Marine antifouling coating compositions.
Background technology
In the evolution of marine economy and shipping interest, marime fouling attachment issue constantly annoyings people.Sea Ocean is stained the consumption of the resistance and fuel that can not only increase ship's navigation, accelerates the corrosion and degradation of hull material, and can break The ecological balance in bad waters.The increasing consumption that Britain international standard paint company was once stained hull bottom with fuel carried out statistics:If hull bottom is dirty Damage 5%, burnup will increase 10%；If hull bottom is stained more than 50%, burnup will increase more than 40%.From on January 1st, 2008, " special efficacy was military Device " Organotin antifouling paints are disabled comprehensively after, gradually form using cuprous oxide as main anti-fouling agent, supplemented by organic anti-fouling agent The formulated coatings system of anti-fouling agent.But even if more and more researchs show the smaller copper ion of toxicity, it still can be in marine organisms Slowly enrichment in vivo, finally generates marine growth huge harm.Some countries have gradually started to limit oxygen at part harbour Change the use of cuprous antifouling paint.
International paint companies fall over each other the antifouling paint without copper Wuxi of development environment close friend.Such as：PPG companies are based on acrylic acid Zinc resin exploitation without copper Tin-free Spc Anti-fouling Paint SIGMA NEXEONTM 750.Some domestic mechanisms are also done in this respect Some researchs, as patent of invention CN104530894A discloses a kind of preparation method of environmentally friendly marine antifouling coating.
The content of the invention
It is an object of the invention to provide a kind of biological antibiotic type acrylic resins.
The present invention also provides a kind of marine antifouling coating compositions, said composition self-cleaning characteristic with high performance and without copper Wuxi, dosage are relatively fewer.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of biological antibiotic type acrylic resin, the resin are made by the raw material as follows in terms of mass fraction：
The biological antibiotic type acrylic resin is compounded by rational component, it is achieved thereby that sterilizing function, environmentally friendly, Without poisonous and harmful substance, waterproof.
Preferably, biological antibiotic type acrylic resin is made by following methods：Equipped with blender, reflux condensing tube, Azodiisobutyronitrile, lauryl mercaptan, butyl acetate are added in the four-hole boiling flask of constant pressure funnel, 100- is warming up to after mixing 110 DEG C, it is different then to add in hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobornyl acrylate, azo two The addition of the mixed liquor of butyronitrile and azobisisovaleronitrile, wherein azobisisovaleronitrile is the 90%-95% of formula ratio, with perseverance Pressure dropping funel through 2.5-3 it is small when constant speed be added dropwise, add the azobisisovaleronitrile of surplus, continue isothermal reaction 0.5- 0.6 it is small when after, be warming up to 110-115 DEG C, when the reaction was continued 2.5-3 is small after, be cooled to room temperature, biological antibiotic is obtained by the reaction in completion Type acrylic resin.By the preparation of this law, a kind of special biological antibiotic type acrylic resin with sterilizing function is obtained, The order of addition and temperature of each raw material, the control of time, to product obtain playing the role of it is vital.Azobisisovaleronitrile Addition at twice, can to avoid by-product generate and obtain properties of product more preferably, quality comparison temperature.
A kind of preparation method of the biological antibiotic type acrylic resin, specifically：Equipped with blender, reflux condensation mode It manages, azodiisobutyronitrile, lauryl mercaptan, butyl acetate is added in the four-hole boiling flask of constant pressure funnel, be warming up to after mixing 100-110 DEG C, then add in hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobornyl acrylate, azo The addition of the mixed liquor of bis-isobutyronitrile and azobisisovaleronitrile, wherein azobisisovaleronitrile is the 90%-95% of formula ratio, With constant pressure funnel through 2.5-3 it is small when constant speed be added dropwise, add the azobisisovaleronitrile of surplus, continue isothermal reaction After when 0.5-0.6 is small, be warming up to 110-115 DEG C, when the reaction was continued 2.5-3 is small after, be cooled to room temperature, biology is obtained by the reaction in completion Antibacterial type acrylic resin.
Marine antifouling coating compositions made from a kind of biological antibiotic type acrylic resin, said composition is by such as Under component in terms of mass fraction be mixed to prepare：
Anti-fouling agent can select the anti-fouling agent of model SeaNine 211.It can also select commercially available similar product.The present invention's Marine antifouling coating compositions are one-component antifouling paints, according to the difference of formula system, can be divided into short-term, medium and long term The antifouling paint of antifouling phase effect.It is verified by long term test, the composition that the present invention compounds has the work(of preferable anti-fouling and self-cleaning Energy.
Preferably, said composition is mixed to prepare by the component as follows in terms of mass fraction：
Side is optimal proportion, and more preferably, dosage is few when being used to the composition of formula as antifouling paint, about general for anti-fouling effect The 20%-30% of logical anti-fouling paint, reduces use cost.
The beneficial effects of the invention are as follows：The present invention is the research and development experience based on environmentally friendly self-cleaning anti-pollution paint peculiar to vessel, ginseng The influence of the biological active matters confrontation marine anti-pollution performance such as Capsaicin has been examined, has synthesized a kind of biological antibiotic type acrylic acid resin, into And it is re-dubbed environmentally friendly marine antifouling coating system.
The invention is characterized in that：(1) a kind of hydroxyl third containing micro biological bactericide is introduced in matrix resin system Olefin(e) acid resin makes resin matrix be provided with sterilization anti-fouling effect；(2) it is a kind of environmental-friendly in formula system without copper Wuxi Type biological antibiotic type antifouling paint；(3) erosive rate of antifouling paint can be adjusted with traditional rosin resin, enhances the interior of paint film Poly- power, technological process are simple and reliable；(4) boric acid is selected to improve the inhibition to marine growth for pH adjusting agent and sterilization inhibitor and make With the comprehensive antifouling capacity for improving coating；(5) polishing speed and biology of antifouling paint are further improved using terpene resin Bactericidal property；(6) adhesive force of resin is improved using the butadiene-styrene rubber adhesive of high molecular weight.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.It should be appreciated that this hair Bright implementation is not limited to the following examples, the accommodation in any form of make the present invention and/or changing all fall Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly used in the art.Method in following embodiments is the normal of this field unless otherwise instructed Rule method.
The synthesis of 1 biological antibiotic type acrylic resin (PAA) of embodiment
The formula of biological antibiotic type acrylic resin is shown in Table 1, equipped with blender, reflux condensing tube, constant pressure funnel Four-hole boiling flask in add in 0.2g azodiisobutyronitriles (AIBN), 2.0g lauryl mercaptans, 200g butyl acetates, be warming up to after mixing It 100 DEG C, then weighs comprising 12g hydroxy-ethyl acrylates, 37g acrylic acid trichlorine phenyl ester, 100g butyl acrylates, 51g acrylic acid The mixed liquor of isobornyl thiocyanoacetate, 1.7g azodiisobutyronitriles and 1.7g azobisisovaleronitrile, with constant pressure funnel through 3 it is small when constant speed Be added dropwise, add 0.1g azobisisovaleronitrile, continue isothermal reaction 0.5 it is small when after, be warming up to 110 DEG C, the reaction was continued 2.5 It after hour, is cooled to room temperature, completes reaction.Reaction scheme is as shown below：
It is detected through IR and GPC, the biological antibiotic type acrylic resin double bond of the present embodiment polymerize completely, number-average molecular weight MnFor 7128, weight average molecular weight 16964, polydispersity coefficient Mw\MnFor 2.38.
The raw material that embodiment 1-3 is used is shown in Table 1.
Table 1
Embodiment 1 2 3
Azodiisobutyronitrile 1.7 1.9 1.5
Azobisisovaleronitrile 1.8 2 1.6
Lauryl mercaptan 2.0 3 5
Butyl acetate 200 200 200
Hydroxy-ethyl acrylate 12 15 10
Acrylic acid trichlorine phenyl ester 37 39 42
Butyl acrylate 100 110 115
Isobornyl acrylate 51 50 45
The synthesis of embodiment 2-3 biological antibiotic type acrylic resins (PAA)
The formula of biological antibiotic type acrylic resin is shown in Table 1, and specific method is the same as embodiment 1, wherein raw material azo diisoamyl Nitrile is put at twice, and the addition of first time azobisisovaleronitrile is the 90%-95% of formula ratio, second of idol for adding in surplus Nitrogen diisoamyl nitrile.
Embodiment 4
A kind of marine antifouling coating compositions, the formula composition of said composition are shown in Table 2.Ocean is made after each raw material is mixed Antifouling paint.According to the difference of formula system, the antifouling paint of the short-term antifouling phase effect of medium and long term can be divided into.
2 (unit of table：kg)
Note：Short-term antifouling phase effect is 1 year, and mid-term is 2 years, is 3-5 for a long time.
After testing, antifouling paint quality index testing result of the invention is as shown in table 3：
Table 3
Inspection project Measured result The method of inspection
Adhesive force/grade ≤2 GB/T1720-79
Impact resistance/(kgcm) ≥45 GB/T1732-93
Flexibility/mm ≤2 GB/T1731-79
Oil resistivity (room temperature, 30d) Coating is unchanged GB/T1734-93
It is tested through real extra large (2 years) cycle of hanging plate 2, short-term antifouling paint, biological attachment amount is less than 5% within 1 year.Medium phase effect 2 years biological attachment amounts of antifouling paint are less than 10%.2 years biological attachment amounts of long-acting and anti-fouling coating are less than 5%, show above-mentioned formula tool There is good anti-fouling effect.
As shown in Table 3, marine antifouling coating of the invention self-cleaning characteristic with high performance, compared with similar products, this Product is without copper Wuxi, and VOC content is low, and environmental pollution is small.The characteristic of this product Primary resins carries out antifouling, antifouling paint dosage Seldom, it is about the 20%-30% of common anti-fouling paint, has saved antifouling paint, reduced use cost.This product can adjust tree The proportioning of fat prepares the different antifouling paint of antifouling phase effect, it is made to be applied to a variety of antifouling fields.
Embodiment described above is a kind of preferable scheme of the present invention, and not the present invention is made in any form Limitation also has other variants and remodeling on the premise of without departing from the technical solution recorded in claim.

Claims (5)

1. a kind of biological antibiotic type acrylic resin, it is characterised in that the resin is by the raw material system as follows in terms of mass fraction ：
Azodiisobutyronitrile 0.35-0.45%,
Azobisisovaleronitrile 0.38-0.48%,
Lauryl mercaptan 0.49-1.2%,
Butyl acetate 47-50%,
Hydroxy-ethyl acrylate 2.3-3.6%,
Acrylic acid trichlorine phenyl ester 9-10%,
Butyl acrylate 24-28%,
Isobornyl acrylate 10-13%.
2. biological antibiotic type acrylic resin according to claim 1, it is characterised in that：Equipped with blender, returned cold It is solidifying to manage, azodiisobutyronitrile, lauryl mercaptan, butyl acetate are added in the four-hole boiling flask of constant pressure funnel, it is warming up to after mixing 100-110 DEG C, then add in hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobornyl acrylate, azo The addition of the mixed liquor of bis-isobutyronitrile and azobisisovaleronitrile, wherein azobisisovaleronitrile is the 90%-95% of formula ratio, with perseverance Pressure dropping funel through 2.5-3 it is small when constant speed be added dropwise, add the azobisisovaleronitrile of surplus, continue isothermal reaction 0.5- 0.6 it is small when after, be warming up to 110-115 DEG C, when the reaction was continued 2.5-3 is small after, be cooled to room temperature, biological antibiotic is obtained by the reaction in completion Type acrylic resin.
3. a kind of preparation method of biological antibiotic type acrylic resin described in claim 1, it is characterised in that：Equipped with stirring Device, reflux condensing tube, constant pressure funnel four-hole boiling flask in add in azodiisobutyronitrile, lauryl mercaptan, butyl acetate, mixing After be warming up to 100-110 DEG C, then add in hydroxy-ethyl acrylate, acrylic acid trichlorine phenyl ester, butyl acrylate, isobomyl acrylate The addition of the mixed liquor of ester, azodiisobutyronitrile and azobisisovaleronitrile, wherein azobisisovaleronitrile is the 90%- of formula ratio 95%, with constant pressure funnel through 2.5-3 it is small when constant speed be added dropwise, add the azobisisovaleronitrile of surplus, it is anti-to continue constant temperature After when answering 0.5-0.6 small, be warming up to 110-115 DEG C, when the reaction was continued 2.5-3 is small after, be cooled to room temperature, life is obtained by the reaction in completion Object antibacterial type acrylic resin.
4. marine antifouling coating compositions made from a kind of biological antibiotic type acrylic resin according to claim 1, Being characterized in that said composition is mixed to prepare by the component as follows in terms of mass fraction：
Biological antibiotic type acrylic resin 10-30%
Terpene resin 2-10%
Rosin resin 2-16%
Butadiene-styrene rubber binder 2-12%
Zinc pyrithione 3-10%
Zineb 3-10%
Triphenylboron pyridine 3-10%
211 3-10% of anti-fouling agent SeaNine
Boric acid 3-12%
Zinc oxide 5-12%
Iron oxide red 2-8%
Polyamide wax pulp 2-6%.
5. marine antifouling coating compositions according to claim 4, it is characterised in that said composition is by as follows with quality The component of fraction meter is mixed to prepare：
Biological antibiotic type acrylic resin 10-30%
Terpene resin 8-10%
Rosin resin 5-16%
Butadiene-styrene rubber binder 10-12%
Zinc pyrithione 3-5%
Zineb 3-10%
Triphenylboron pyridine 3-5%
211 3-10% of anti-fouling agent SeaNine
Boric acid 10-12%
Zinc oxide 5-12%
Iron oxide red 4-8%
Polyamide wax pulp 3%.
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CN106519837B (en) * 2016-10-08 2018-11-02 江苏冶沪建筑科学研究院有限公司 A kind of hull bottom long-acting and anti-fouling coating and preparation method thereof
CN108610449B (en) * 2017-01-14 2021-03-12 浙江省海洋开发研究院 Para-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and novel marine antifouling paint prepared from same
CN109762098B (en) * 2018-12-29 2021-01-01 浙江省海洋开发研究院 Linear self-polishing antifouling resin rich in biological bactericide and copper-free marine antifouling paint containing resin
CN109836951B (en) * 2019-01-17 2021-01-05 浙江省海洋开发研究院 Copper-containing linear self-polishing marine antifouling paint
CN110452596B (en) * 2019-07-24 2020-07-24 武汉理工大学 Organic silicon modified zinc acrylate/zinc pyrithione composite antifouling paint and preparation method and application thereof
CN110724424B (en) * 2019-10-14 2022-03-25 浙江海洋大学 Antifouling coating for marine mesh wire and preparation method thereof
CN111253821B (en) * 2019-10-31 2022-03-22 浙江省海洋开发研究院 High-solid-content copper-free linear self-polishing marine antifouling paint
CN114702627B (en) * 2022-04-27 2023-07-21 南方海洋科学与工程广东省实验室(湛江) Degradable polymer and preparation method and application thereof

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CN102558989A (en) * 2010-12-09 2012-07-11 海洋化工研究院 Anti-fouling coating material with excellent compatibility and use thereof
CN104293062A (en) * 2014-09-12 2015-01-21 浙江省海洋开发研究院 Aqueous soft biomass anti-fouling paint and preparation method thereof

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